Radiative relaxation in isolated large carbon clusters: Vibrational emission versus recurrent fluorescence

Recurrent fluorescence (RF) from isolated carbon clusters containing between 24 and 60 atoms is theoretically investigated as a function of internal energy, cluster size, and structural features. The vibrational relaxation kinetics and the associated IR emission spectra are determined by means of a Monte Carlo approach with vibrational density of states computed in the harmonic approximation. RF is generally found to be highly competitive with vibrational emission. The behaviors predicted for clusters of various sizes and archetypal structures indicate that the IR emission spectra are strongly influenced by RF, an energy gap law being obtained for the evolution of the RF rate constant depending on the electronic excitation state. The present results are relevant to the photophysics of the interstellar medium and could contribute to elucidating the carriers of the extended red emission bands and the continuum emission lying below the aromatic infrared bands believed to originate from mixed aromatic-aliphatic compounds.